Pd-Catalyzed Cascade Crossover Annulation of <i>o</i>‑Alkynylarylhalides and Diarylacetylenes Leading to Dibenzo[<i>a</i>,<i>e</i>]pentalenes

A novel and selective Pd-catalyzed cascade crossover-annulation of o-alkynylarylhalides and diarylacetylenes for the synthesis of dibenzo­[a,e]­pentalenes has been reported. Various arylacetylenes with a wide range of functional groups were tolerated, producing the corresponding multisubstituted dibenzopentalenes with the different substituents on the aromatic rings in good to high yields under the optimized reaction conditions. The reaction proceeds through a Pd-catalyzed cascade carbopalladation and C–H activation. The use of the combined DBU and CsOPiv bases is crucial for the successful implementation of the present cross-annulation.